Anion Effects in Organic Dye-Sensitized Mesoscopic Solar Cells with Ionic Liquid Electrolytes: Tetracyanoborate vs Dicyanamide

We compare the impacts of tetracyanoborate and dicyanamide anions in solvent-free ionic liquid electrolytes upon the optoelectronic features of dye-sensitized solar cells based on an organic push-pull chromophore. With respect to dicyanamide, tetracyanoborate confers a bathochromic and higher photocurrent response upon a dye-coated mesoporous titania film. Numerical simulations on electrical impedance spectroscopies disclose that tetracyanoborate anion S evoke a downward displacement of the conduction-band edge of an electrolyte-sinking nanocrystalline film in comparison with dicyanamide, generating a more favorable energy-offset at the titania/dye interface and therefore a better exciton dissociation yield, as proved via the transient emission measurements. An effective recombination reaction rate constant U-0k is used to depict the charge-transfer behavior at the titania/electrolyte interface in dye-sensitized solar cells. The negative impact of an about 4 times larger U-0k of the dicyanamide cell is overwhelmed by the noticeably higher conduction band edge, leading to the experimentally observed anion-dependent open-circuit photovoltage.